水溶性高分子量聚苯乙烯磺酸钠的制备

水溶性聚苯乙烯磺酸钠(PSS)是一种具有良好表面活性作用的高分子,近年来主要应用在碳纳米管的表面改性[1-2],工业废水处理中的助凝剂[3-4],聚合物接枝改性[5],晶体形貌生长调节剂[6-7],混凝土减水剂[8]等领域.     

Graft copolymers composed of high molecular weight poly(ethylene oxide) backbone and poly(N-isopropylacrlylamide) side chains and their thermoassociating properties

Novel, water-soluble thermoassociative graft copolymers based on high molecular weight (HMW) poly(ethylene oxide-co-glycidol) backbone and relatively short grafts of poly-N-isopropyl acrylamide (NIPAAm) were prepared. The copolymer precursors with two architectures (block and graft) were synthesized using Ca-amide-alkoxide initiators. The OH groups in the copolymer precursors have been utilized for grafting NIPAAm using ceric ion (Ce⁴⁺) redox initiation. The idea was to imprint the “smart” properties of PNIPAAm grafts into common HMW poly(ethylene oxide). The sensitive moieties undergo reversible association transitions by changing the temperature of dilute and semidilute aqueous solutions of the copolymers. Associative properties were studied by viscosity and rheology measurements. Two types of interactions, induced by heating, depending on the copolymer concentration namely intra- and intermolecular association were observed.     

Dissipative crystallization of sodium salts of poly (d-glutamic acid), poly (l-glutamic acid), and their low molecular weight analogs

Drying dissipative patterns were observed at room temperature on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous solution of sodium salts of poly (d-glutamic acid), poly (l-glutamic acid), and their low molecular weight analogs, monosodium d-glutamate, monosodium l-glutamate, and monosodium dl-glutamate. The low molecular weight analogs were hygroscopic and their drying patterns were observed in a dry box coexisted with the bags of desiccant. The broad rings, which are the typical macroscopic drying patterns, were observed for all the samples. Optical isomeric effects on the drying patterns were not recognized. Spherulite (or hedrite) and rod-like crystals from the assemblies of helical main chains of the polymers are formed mainly at the inner area from the broad ring (except central area) and the broad ring area, respectively. Coexistence of sodium chloride enhanced the crystal structures by the cooperative interactions between the polymers and the salts. The typical dissipative crystallization such as accumulation, segregation, and orientation effects of crystals were observed in the drying patterns.     

Surface properties of poly(acrylonitrile) (PAN) precipitation polymerized in supercritical CO2 and the influence of the molecular weight

In this paper, the surface properties, e.g., the total surface free energy and the related Lifshitz-van der Waals and Lewis acid-base components, of polyacrylonitrile (PAN) precipitation polymerized in supercritical CO(2) have been characterized. Moreover, the influence of molecular weight varying has been also investigated. Results show that the surface properties of PAN resulting from supercritical CO(2) are different from those obtained by the conventional method. Of these data, one important finding is that the supercritical CO(2) PAN seems to decrease the surface free energy with the increased molecular weight. Based on previous recorded NMR spectra of this PAN and especially compared to commercial PAN, such phenomena are discussed and ascribed to an increase of the H-bonds and a reduction of the isotacticity in the supercritical CO(2) condition for PAN.     

Preparation of quinolinium salts differing in the length of the alkyl side chain

Quaternary quinolinium salts differing in alkyl chain length are members of a widespread group of cationic surfactants. These compounds have numerous applications in various branches of industry and research. In this work, the preparation of quinoline-derived cationic surface active agents differing in the length of the side alkyl chains (from C? to C??) is described. An HPLC method was successfully developed for distinction of all members of the series of prepared long-chain quinolinium derivatives. In conclusion, some possibilities of intended tests or usage have been summarized. In vitro testing using a microdilution broth method showed good activity of a substance with a C12 chain length against Gram-positive cocci and Candida species.     

Effect of Molecular Weight on the Properties of Poly（butylene succinate）

Poly（butylene succinate） （PBS） with different molecular weight was synthesized from 1, 4-butanediol and succinic acid by direct melt condensation. The synthesized PBS was identified by IH-NMR and FTIR spectrometry. The molecular weight was calculated from the intrinsic viscosity, and its value was between 20000 and 70000. The crystallization behavior and crystal morphology as function of molecular weight were investigated by DSC and PLM, respectively. The mechanical properties and hydrolytic degradation behaviors related with change of molecular weight were also studied in this work. The results demonstrated that the properties of PBS were determined by both molecular weight and crystallization properties （crystallinity as well as crystal morphology）. Our work is important for the design and preparation of PBS with proper molecular weight for its practical application.     

Preparation of benzalkonium salts differing in the length of a side alkyl chain

Benzalkonium salts are widely used as disinfectants, biocides and detergents,among a variety of other applications. The cationic surface-activity of these salts determines their potential to act as a biocide on both target and non-target organisms. In this study, a quick synthesis of a complete set of the benzalkonium salts differing in the length of an alkylating chain (from C(2) to C(20)) is described. Moreover, their (1)H-NMR, HPLC-MS, TLC and HPLC analysis were recorded.     

Viscoelastic properties of amorphous polymers 3: low molecular weight poly(methylphenylsiloxane)

By making creep and recoverable creep measurements of a nearly monodisperse low molecular weight poly(methyl phenyl siloxane) sample, we have found on decreasing temperature towardsT _g that there is continuously a change in the viscoelastic spectrum concomitant with a decrease of the steadystate recoverable compliance. This behavior is exactly the same as previously observed in low molecular weight poly(styrene), proving that this spectacular anomaly in the viscoelasticity of low molecular weight polymers is general and deserves an explanation. Photon correlation spectroscopic measurements performed on the same sample have extended the observation of the viscoelastic response to shorter times and the result corroborates the trend of variation established by the creep data.Dedicated to Prof.Dr. E. W. Fischer on his 65th Birthday. Prof.Dr. Fischer is known for his valuable contribution to fosterine, international collaboration of research in polymer science. This work is an example of his contribution because it would not be possible without him bringing us together. One of us (KLN) would like to take this opportunity to thank Prof. Dr. Fischer for his unwaiving support of the 1st (Crete) and the 2nd (Alicante) International Discussion Meeting on Relaxations in Complex Systems     

Conformational change of poly(L-lysine) and poly(L-ornithine) and cooperative binding of sodium alkanesulfonate surfactants with different chain length

Conformations of poly(L-lysine) (PLL) and poly(L-ornithine) (PLO) were examined in aqueous solutions of sodium alkanesulfontates (C_nSO₃Na, n=9, 10, 11, 12) in the presence of 0.02 M NaCl by circular dichroism (CD) spectroscopy. These surfactants induce the-structure for PLL and the-helix for PLO. The binding of surfactants on the polypeptides was measured potentiometrically with a surfactant ion electrode and was found to be highly cooperative. The cooperativity increases with increasing chain length of surfactant. The behavior accompanying the surfactant binding and the conformational change indicated that the conformational change requires a certain amount of bound surfactants in the case of C₉SO₃Na and starts immediately on binding of surfactant in the case of C_{1 2}SO₃Na. The clustering of bound surfactants due to the cooperative binding as well as neutralization of polypeptides contributes to their conformational change. A slow conformational change of PLO was found in the time scale of hours, sometimes days, for C₉- and C₁₀SO₃Na at low concentrations, but the binding process reached the equilibrium quickly. This slow mode might occur due to the slow interaction between surfactant/polypeptide complexes.     

Synthesis and properties of polymer brushes composed of poly(diphenylacetylene) main chain and poly(ethylene glycol) side chains

Novel cylindrical polymer brushes consisting of poly(diphenylacetylene) main chain and poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) side chains were synthesized by the diphenylacetylene macromonomer or side chain initiated atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether monomethacrylate (PEGMA) from an bromo isobutyryl-bearing poly(diphenylacetylene) (poly(BrDPA)) method. The diphenylacetylene macromonomer, namely, DPA-PPEGMA, were prepared by the ATRP of PEGMA from bromo isobutyryl-bearing diphenylacetylene. DPA-PPEGMA was polymerized successfully with WCl₆-Ph₄Sn catalyst to give high molecular weight polymer brushes poly(DPA-PPEGMA). Meanwhile, polymer brushes (PDPA-g-PPEGMA) were obtained by ATRP of PEGMA from poly(BrDPA). The molecular weight of the side chains of PPEGMA could be controlled simply by modulating the ATRP time. The macromonomer and polymer brushes are soluble in nonpolar solvents such as toluene and chloroform. The polymers of poly(BrDPA) and poly(DPA-PPEGMA) absorb in the longer wavelength region, with two peaks at around 370 and 414 nm. The polymers are thermally stable and exhibit double crystallization and melting peaks during the cooling and heating scans.     

Formation and surface properties of raspberry-like silica particles: effect of molecular weight of the coating poly(methacrylic acid) brushes

In this work, silica particles were firstly modified with poly(methyl methacrylate) and then converted to poly(methacrylic acid) (PMAA). The PMAA brushes with different molecular weight were used to modify the seed particles and learn the formation process of the raspberry-like particles. Silica particles with core–shell structure were obtained when the silica seed particles were modified only with carboxyl functional groups. With the increase of the molecular weight of PMAA brushes, uniform raspberry-like silica particles appeared gradually. But when the molecular weight of PMAA brushes was above 136,100, the morphologies became complicated. The electric charge of the polymer brushes was also found to have influence on the final morphologies of the particles. The contact angle (CA) tests showed that films composed of nanoparticles with uniform raspberry-like structures had an average CA of 157.2°, which indicated great prospects in the super-hydrophobic applications.     

Effect of branching and molecular weight on the viscoelastic properties of poly(butyl acrylate)

A series of poly(butyl acrylate) samples were prepared by emulsion polymerization with a range of molecular weights and degrees of chain branching. Characterization was performed with NMR (giving the fraction of branching, ranging from approximately 0 to 7%), gel permeation chromatography, viscometry, and determination of the gel fraction. The dynamic mechanical response, that is, the frequency dependence of the storage and loss moduli G′(ω) and G″(ω) was measured from 0.02 to 200 Hz. The occurrence of a significant insoluble fraction in the sample meant that full characterization of the molecular weight distribution was not possible, and so an unambiguous separation of the dependencies of the mechanical response on the degree of long‐chain branching (LCB) and short‐chain branching (SCB) and the molecular weight could not be made; however, trends dependent on the molecular weight alone were insufficient to model the results. At high frequencies, all trends in G′(ω) and G″(ω) could be ascribed to molecular weight dependencies; at low frequencies, the effects of both the molecular weight and total degree of branching could be inferred, with more highly branched samples showing lower storage and loss moduli. Although the relative amounts of SCB and LCB could not be determined, no dynamic features attributable to LCB were observed. The low‐frequency trends could be semiquantitatively fitted with reptation and retraction theory if it was assumed that an increased degree of SCB led to an increased tube size. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3335–3349, 2002     

Influence of molecular weight on the dynamic mechanical properties of poly(methyl methacrylate)

Using a new parallel beam apparatus, the dynamic mechanical properties of poly-(methyl methacrylate) were determined over a wide range of molecular weights (1500< < <600 000). Results showed that the modulus (25 °C) was only slightly dependent on chain length, and equalled 2.3×10⁹ Pa for the highest molecular weight scanned. Simultaneous acquisition of- and-relaxations indicated a decrease inT in accordance with Gibbs' relation, whileT was invariant. BothT =111° andT =40° corroborated previous results from several sources, including dynamic mechanical measurements. Such modulus and glass transition data are essential to the calculation of fracture toughness and to the assessment of radiation damage of acrylic, respectively.

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Zusammenfassung Unter Anwendung eines neuen Parallelstrahlgerätes wurden die dynamischen mechanischen Eigenschaften von Poly(methylmethacrylat) in einem weiten Molmassenbereich (1500< <600 000) bestimmt. Die Ergebnisse zeigten, daß der Modul (25°) nur wenig von der Kettenlänge abhängig und für die höchste erfaßte Molmasse gleich 2.3× ×10⁹ Pa war. Die gleichwertige Erfassung der- und-Relaxationen zeigte in Übereinstimmung mit der Gibbs-schen Abhängigkeit eine Abnahme vonT währendT unverändert blieb. SowohlT =111° als auchT =40° bestätigten frühere Ergebnisse verschiedenen Ursprungs, dynamische mechanische Messungen mit inbegriffen. Solch ein Modul und Glas-Übergangsdaten sind zur Berechnung der Bruchfestigkeit bzw. zur Bestimmung der Bestrahlungsschäden in Acrylaten unerläßlich.

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Résumé En se servant d'un nouvel appareil à rayons parallèles, on a déterminé les propriétés mécaniques dynamiques du poly(méthyl-méthacrylate) dans un large intervalle de poids moléculaires (1500< <600 000). Les résultats on montré que le module (25°) ne dépend que peu de la longueur de la chaîne et est égal à 2.3×10⁹ Pa pour le plus haut poids moléculaire étudié. L'acquisition simultanée des relaxations et a indiqué, en accord avec la relation de Gibbs, une diminution deT tandis queT s'avere invariable. Les valeursT =111°et}T =40° ont corroboré toutes deux des résultats antérieurs de diverses sources, y compris des mesures mécanique dynamiques. Un tel module ainsi que les données de la transition vitreuse sont essentiels pour calculer la résistance à la rupture, et pour déterminer les dommages par irradiation des matières acryliques.

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, (1500 < < 600 000). , (25°) 2.3&#x0445;10⁹ . - - T , T . T =111° T =40° , . .

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This investigation was supported by NIH Research Grant No. DE 02668, RCDA number DE 00052 (R.P.K.), and RFA number DE 05132 (A.R.G.).     

Transport properties of solid polymer electrolytes prepared from oligomeric fluorosulfonimide lithium salts dissolved in high molecular weight poly(ethylene oxide)

Transport properties such as ionic conductivity, lithium transference number, and apparent salt diffusion coefficient are reported for solid polymer electrolytes (SPEs) prepared using several oligomeric bis[(perfluoroalkyl)sulfonyl]imide (fluorosulfonimide) lithium salts dissolved in high molecular weight poly(ethylene oxide) (PEO). The salt series consists of polyanions in which two discrete fluorosulfonimide anions are linked together by [(perfluorobutylene)disulfonyl]imide linker chains. The restricted diffusion technique was used to measure the apparent salt diffusion coefficients in SPEs, and cationic transference numbers were determined using both potentiostatic polarization and electrochemical impedance spectroscopy methods. A general trend of diminished salt diffusion coefficient with increasing anion size was observed and is opposite to the trend observed in ionic conductivity. This unexpected finding is rationalized in terms of the cumulative effects of charge carrier concentration, anion mobility, ion pairing, host plasticization by the anions, and salt phase segregation on the conductivity.     

Aggregation of poly(1,3‐cyclohexadiene): Effects of molecular weight and polymer chain structure

The aggregation of poly(1,3‐cyclohexadiene) (PCHD), obtained by anionic polymerization with alkyllithium/amine systems, was examined using size exclusion chromatography (SEC) and size exclusion chromatography coupled with a multiangle laser light scattering photometer (SEC‐MALS). The PCHD polymer chain has a structure consisting of a main chain formed by 1,2‐addition (the 1,2‐CHD unit) and 1,4‐addition (the 1,4‐CHD unit). Mild stirring with relatively low temperature in the polymerization reaction forms an aggregation of PCHD. The molecular weight and molar ratio of 1,2‐CHD/1,4‐CHD units in the polymer chain strongly influence the aggregation of PCHD. In a high molecular weight PCHD, containing ～50% 1,2‐CHD units, an aggregation of the polymer was observed in tetrahydrofuran (THF) solution at room temperature. This aggregation of PCHD was soluble in 1,2,4‐trichlorobenzene (TCBz) and could be separated into each polymer molecule. In contrast, a polymer chain with a high content of 1,4‐CHD units having a relatively low cis‐stereospecificity was easily soluble in THF and TCBz without aggregating. A long polymer chain structure with a high content of 1,2‐CHD units is considered to be the reason for the generation of strong intermolecular forces contributing to the aggregation of PCHD with the solvophobic interactions. The degree of aggregation could be controlled by the conditions of the PCHD polymer solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1442–1452, 2006     

Effect of alkyl side chain length on the properties of polyetherimides from molecular simulation combined with experimental results

Three polyetherimides (PEIs) with the same backbone of Ultem 100 but different lengths of the alkyl side chains were simulated by using molecular dynamics and molecular mechanics techniques to investigate the effect of side chain length on their properties and physical mechanism behind. Simulation results, which are consistent to the experimental data, show that PEI‐5 with four methylene units in each alkyl side chain has higher T_g (glass transition temperature) and higher tensile strength, but lower tensile elongation at break than those of PEI‐6 with five and PEI‐8 with seven methylene units in each alkyl side chain. However, unlike the traditional phenomena, conformational analysis provides that PEI‐5 with the highest T_g gives the highest flexibility to the polymer chain, whereas PEI‐8 with the lowest T_g imparts the lowest flexibility resulting from attachment of longer alkyl side chain increase the rigidity of backbone. From the calculated ratio of the accessible volume to the total volume for each system, the highest ratio of PEI‐8 indicates that long alkyl side chains generate more free volume than short side chains, acting as an internal plasticizer in bulk structure. It is the internal plasticizing effect that is predominantly responsible for the abnormal properties, instead of the rigidity from side chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 595–599, 2010     

Phase behavior of cationic hydroxyethyl cellulose-sodium dodecyl sulfate mixtures: effects of molecular weight and ethylene oxide side chain length of polymers

Novel cationic hydroxyethyl cellulose (HEC) polymers with different molecular weights (1.1 x 10(5) to 1.7 x 10(6) g/mol) and ethylene oxide (EO) side chain lengths (1.5-2.9 EO units) were mixed with sodium dodecyl sulfate (SDS) in aqueous solutions. The phase diagrams of cationic HEC-SDS complexes were determined in the dilute polymer concentration regime (< 0.5 wt %) with gradual addition of SDS molecules. The viscosity and structures of the complexes during the phase evolution were studied using rheometry and dynamic light scattering. The gradual addition of SDS first induced interchain associations with the bound SDS aggregates serving as cross-linkers to form an open network structure, producing a very broad size distribution and high viscosities of the complex solutions, and then condensed the network and induced a structure reorganization, resulting in globular aggregates with narrow size distributions. The growth of these globular aggregates in size eventually led to macroscopic sedimentation near charge neutralization. Further addition of SDS randomly broke the sedimentary aggregates into small particles and SDS micelles with low solution viscosities. The effects of molecular weight and EO side chain length of polymers on the phase boundary, viscosity, and structure of cationic HEC-SDS complexes were discussed.     

Preparation of high molecular weight poly(vinylaniline)

For the first time, we believe, a high molecular weight soluble poly(vinylaniline) has been prepared. This was done by a bead polymerization with exclusion of oxygen. The polymer has little or no color and good stability in solution.     

Effect of chain length on the interaction between modified organic salts containing hydrocarbon chains and poly(N-isopropylacrylamide-co-acrylic acid) microgel particles

A series of four hydrophobically modified, diphenylazo-based organic salts have been prepared and characterized. To achieve this a C(x) (x = 4, 6, 8, or 10) hydrocarbon chain was inserted between the diphenylazo moiety and the quaternary ammonium headgroup of the salt. The absorption of each of the four modified organic salts into anionic microgel particles of poly(N-isopropylacrylamide-co-acrylic acid) has been studied at pH 8. In addition, the hydrodynamic diameters and electrophoretic mobilities of the microgel particles have been studied as a function of the organic salt concentration, also at pH 8. In addition to the electrostatic attraction between the quaternary ammonium head groups of the organic salts and the anionic groups within the microgel particles, hydrophobic association between the chains of the organic salts within the microgel particles plays a role, with this effect increasing strongly from x=4 to 10. Desorption of the x=4 and 6 organic salts occurs readily on changing, in situ, the pH from 8 to 2.5 (and thereby eliminating the electrostatic interaction) but is only partially achieved for the x=8 and 10 organic salts. Indeed, for the x=10 organic salt, only about 80% of the organic salt is desorbed upon dilution of the microgel particles into a large excess of water.